The nonadiabaticity question for europium(III/II)

Outer-sphere reactivities of europium(III/II) cryptates

Edmund L. Yee, Joseph T Hupp, Michael J. Weaver

Research output: Contribution to journalArticle

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Abstract

The one-electron reduction kinetics of the europium cryptates Eu(2.2.1)3+ and Eu(2.2.2)3+ by the aquo ions Vaq 2+ and Euaq 2+ and the oxidation kinetics of Eu(2.2.1)2+ by Co(NH3)6 3+ have been studied by using a polarographic technique in order to examine the effects of encapsulating europium within cryptate cavities upon the reactivity of the Eu(III/II) couple. At 25°C and an ionic strength μ = 0.1, the second-order rate constants (M-1 s-1) for acid-independent pathways are as follows: Eu(2.2.1)3+-Vaq 2+, 0.5; Eu(2.2.1)3+-Euaq 2+, ca. 0.2; Eu(2.2.2)3+-Euaq 2+, 1.5; Eu(2.2.2)3+-Euaq 2+, 1.4; Co(NH3)6 3+-Eu(2.2.1)2+, 0.055. By comparison of these kinetic data with those for similar reactions involving the Euaq 3+/2+ couple, the rate constant for Eu(III/II) self-exchange, kex, is estimated to increase by factors of ca. 1 × 107 and 2 × 104 upon encapsulation of europium in (2.2.1) and (2.2.2) cryptate cavities, respectively. Estimates of kex equal to ca. 10, 4 × 10-2, and 5 × 10-6 M-1 s-1 (μ = 0.1) for Eu(2.2.1)3+/2+, Eu(2.2.2)3+/2+, and Euaq 3+/2+, respectively, are obtained from the Marcus cross relation. The increases in kex resulting from cryptate encapsulation suggest that nonadiabaticity is not primarily responsible for the extremely low reactivity of Euaq 3+/2+. The values of kex are shown to be roughly consistent with the Franck-Condon barriers estimated from structural data.

Original languageEnglish
Pages (from-to)3465-3470
Number of pages6
JournalInorganic Chemistry
Volume22
Issue number23
Publication statusPublished - 1983

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Europium
Crown Ethers
europium
reactivity
Encapsulation
Kinetics
Rate constants
kinetics
cavities
encapsulating
Ionic strength
Ions
Oxidation
oxidation
acids
Acids
Electrons
estimates
ions
electrons

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

The nonadiabaticity question for europium(III/II) : Outer-sphere reactivities of europium(III/II) cryptates. / Yee, Edmund L.; Hupp, Joseph T; Weaver, Michael J.

In: Inorganic Chemistry, Vol. 22, No. 23, 1983, p. 3465-3470.

Research output: Contribution to journalArticle

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abstract = "The one-electron reduction kinetics of the europium cryptates Eu(2.2.1)3+ and Eu(2.2.2)3+ by the aquo ions Vaq 2+ and Euaq 2+ and the oxidation kinetics of Eu(2.2.1)2+ by Co(NH3)6 3+ have been studied by using a polarographic technique in order to examine the effects of encapsulating europium within cryptate cavities upon the reactivity of the Eu(III/II) couple. At 25°C and an ionic strength μ = 0.1, the second-order rate constants (M-1 s-1) for acid-independent pathways are as follows: Eu(2.2.1)3+-Vaq 2+, 0.5; Eu(2.2.1)3+-Euaq 2+, ca. 0.2; Eu(2.2.2)3+-Euaq 2+, 1.5; Eu(2.2.2)3+-Euaq 2+, 1.4; Co(NH3)6 3+-Eu(2.2.1)2+, 0.055. By comparison of these kinetic data with those for similar reactions involving the Euaq 3+/2+ couple, the rate constant for Eu(III/II) self-exchange, kex, is estimated to increase by factors of ca. 1 × 107 and 2 × 104 upon encapsulation of europium in (2.2.1) and (2.2.2) cryptate cavities, respectively. Estimates of kex equal to ca. 10, 4 × 10-2, and 5 × 10-6 M-1 s-1 (μ = 0.1) for Eu(2.2.1)3+/2+, Eu(2.2.2)3+/2+, and Euaq 3+/2+, respectively, are obtained from the Marcus cross relation. The increases in kex resulting from cryptate encapsulation suggest that nonadiabaticity is not primarily responsible for the extremely low reactivity of Euaq 3+/2+. The values of kex are shown to be roughly consistent with the Franck-Condon barriers estimated from structural data.",
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N2 - The one-electron reduction kinetics of the europium cryptates Eu(2.2.1)3+ and Eu(2.2.2)3+ by the aquo ions Vaq 2+ and Euaq 2+ and the oxidation kinetics of Eu(2.2.1)2+ by Co(NH3)6 3+ have been studied by using a polarographic technique in order to examine the effects of encapsulating europium within cryptate cavities upon the reactivity of the Eu(III/II) couple. At 25°C and an ionic strength μ = 0.1, the second-order rate constants (M-1 s-1) for acid-independent pathways are as follows: Eu(2.2.1)3+-Vaq 2+, 0.5; Eu(2.2.1)3+-Euaq 2+, ca. 0.2; Eu(2.2.2)3+-Euaq 2+, 1.5; Eu(2.2.2)3+-Euaq 2+, 1.4; Co(NH3)6 3+-Eu(2.2.1)2+, 0.055. By comparison of these kinetic data with those for similar reactions involving the Euaq 3+/2+ couple, the rate constant for Eu(III/II) self-exchange, kex, is estimated to increase by factors of ca. 1 × 107 and 2 × 104 upon encapsulation of europium in (2.2.1) and (2.2.2) cryptate cavities, respectively. Estimates of kex equal to ca. 10, 4 × 10-2, and 5 × 10-6 M-1 s-1 (μ = 0.1) for Eu(2.2.1)3+/2+, Eu(2.2.2)3+/2+, and Euaq 3+/2+, respectively, are obtained from the Marcus cross relation. The increases in kex resulting from cryptate encapsulation suggest that nonadiabaticity is not primarily responsible for the extremely low reactivity of Euaq 3+/2+. The values of kex are shown to be roughly consistent with the Franck-Condon barriers estimated from structural data.

AB - The one-electron reduction kinetics of the europium cryptates Eu(2.2.1)3+ and Eu(2.2.2)3+ by the aquo ions Vaq 2+ and Euaq 2+ and the oxidation kinetics of Eu(2.2.1)2+ by Co(NH3)6 3+ have been studied by using a polarographic technique in order to examine the effects of encapsulating europium within cryptate cavities upon the reactivity of the Eu(III/II) couple. At 25°C and an ionic strength μ = 0.1, the second-order rate constants (M-1 s-1) for acid-independent pathways are as follows: Eu(2.2.1)3+-Vaq 2+, 0.5; Eu(2.2.1)3+-Euaq 2+, ca. 0.2; Eu(2.2.2)3+-Euaq 2+, 1.5; Eu(2.2.2)3+-Euaq 2+, 1.4; Co(NH3)6 3+-Eu(2.2.1)2+, 0.055. By comparison of these kinetic data with those for similar reactions involving the Euaq 3+/2+ couple, the rate constant for Eu(III/II) self-exchange, kex, is estimated to increase by factors of ca. 1 × 107 and 2 × 104 upon encapsulation of europium in (2.2.1) and (2.2.2) cryptate cavities, respectively. Estimates of kex equal to ca. 10, 4 × 10-2, and 5 × 10-6 M-1 s-1 (μ = 0.1) for Eu(2.2.1)3+/2+, Eu(2.2.2)3+/2+, and Euaq 3+/2+, respectively, are obtained from the Marcus cross relation. The increases in kex resulting from cryptate encapsulation suggest that nonadiabaticity is not primarily responsible for the extremely low reactivity of Euaq 3+/2+. The values of kex are shown to be roughly consistent with the Franck-Condon barriers estimated from structural data.

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